Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

• the present invention relates to a method for processing silver halide photographic light-sensitive materials, and more particularly to a method for preventing silver halide photographic light-sensitive materials from producing a fog in the processing thereof.
• stabilizers or fog restrainers to be used for the purpose of preventing silver halide photographic light-sensitive materials (hereinafter called light-sensitive materials) from producing a fog with the lapse of time a large number of compounds including, for example, hydroxypolyazaindenes such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, and azole derivatives such as benzimidazole, benzotriazole, indazole, and the like.
• hydroxypolyazaindenes such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene
• mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole
• azole derivatives such as benzimidazole, benzo
• a method for processing silver halide photographic light-sensitive materials which comprises a developing process in which a silver halide photographic light-sensitive material is developed in the presence of at least one compound having Formula [Ia] or [Ib]: ##STR2## wherein Ar is a benzene ring of a naphthalene ring, each of which rings may be in the quinone form, F is a fluorine atom, Y and Y' each is a substituent substitutable to the benzene ring or naphthalene ring, X is a divalent linkage group, m and m' each is an integer of from 1 to 5, and n and n' each is an integer of from 1 to 3.
• Those compounds having Formulas [Ia] and [Ib] to be used in this invention are required to be of a benzene ring or a naphthalene ring (each of which rings may be in the quinone form) having thereon at least one fluorine atom and at least one substituent (represented by Y and Y') other than the fluorine atom.
• Those groups substitutable to the benzene ring or naphthalene ring represented by Y or Y' include preferably halogen atoms excluding fluorine, mercapto group, carboxyl group and salts thereof, sulfo group and salts thereof, amino group, acylamino groups, alkylamino groups, nitro group, cyano group, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkyl-thio groups, aryl-thio groups, alkoxy-carbonyl groups, carbamoyl group, sulfamoyl group, alkoxyalkyl groups, aminoalkyl groups, acylaminoalkyl groups, hydroxyalkyl groups, carboxyalkyl groups, sulfoxalkyl groups, alkylsulfonamidoalkyl groups, and the like.
• hydrophilic groups including, e.g., the hydroxyl group, mercapto group, carboxyl group and salts thereof, sulfo group and salts thereof, and the like.
• examples of the divalent linkage group represented by the X although not restricted either, include, e.g., --O--, --S--, --S--S--, --(CH 2 ) l -- (l is an integer of from 1 to 8), and the like.
• the development of a light-sensitive material is made in the presence of a compound having Formula [Ia] or [Ib] (those having both Formulas will be hereinafter called the "compound of Formula [I]” or the “antifoggant of this invention”) means more particularly either a method in which a light-sensitive material containing the compound of this invention in at least one of the component layers thereof such as the silver halide emulsion layer and/or a layer adjacent thereto, filter layer, antihalation layer, protective layer, subbing layer, etc., is developed, or a method in which the development of a light-sensitive material is carried out in a developer solution or a bath prior to the developing process into which is incorporated the compound of this invention.
• the particularly preferred one of these methods is the former; i.e., the method in which the compound of this invention is incorporated into the emulsion layer of a light-sensitive material.
• the adding amount of the antifoggant of this invention where added to the silver halide emulsion layer of a light-sensitive material, is desirable to be used in the range of from 1 ⁇ 10 -5 to 1 ⁇ 10 -1 mole per mole of the silver halide contained in the emulsion layer, and more preferably from 1 ⁇ 10 -5 to 1 ⁇ 10 -4 mole, and, where added to a non-light-sensitive layer, is desirable to be used in the range of from 1 ⁇ 10 -5 to 1 ⁇ 10 -1 mole per m 2 .
• the adding amount is preferably in the range of from 10 -5 to 10 -1 mole, and more preferably from 10 -4 to 10 -2 mole.
• the compound of this invention may be dissolved in a solvent miscible with water, such as methanol, ethanol, dimethylformamide, or in an aqueous alkaline solution, and the solution of the compound may be then incorporated into the foregoing component layer(s) of a light-sensitive material or into the foregoing developer solution.
• a solvent miscible with water such as methanol, ethanol, dimethylformamide, or in an aqueous alkaline solution
• any known method may be used except for the presence of the compound of this invention.
• the processing may be made at a temperature of from 18° C. to 50° C. According to purposes, any of the black-and-white photograph processing, lith-type developing process, or color photograph processing to form dye images may apply to the processing method.
• Examples of the developing agent for the black-and-white photograph processing include dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), aminophenols (such as N-methyl-p-aminophenol), ascorbic acid, and the like. These compounds may be used alone or in combination.
• the developer solution may contain other known preservative, alkaline agent, pH buffer, fog restrainer, etc., and further, if necessary, solvent, tone control agent, development accelerator, surfactant, defoaming agent, water softener, hardening agent, and the like.
• the present invention may also apply to a light-sensitive material of the type of containing a developing agent and of being processed in an alkaline bath; i.e., the so-called agent-in-emulsion-type light-sensitive material.
• a color developing agent-containing aqueous alkaline solution may be used.
• the color developing agent any of those known primary aromatic amine developers such as phenylenediamines may be used.
• the color developer solution may, in addition to the above agent, also contain a pH buffer such as a sulfite, carbonate or borate of an alkali metal, a halogen salt or organic antifoggant, a water softener, a preservative, an organic solvent such as benzyl alcohol, ethylene glycol, etc., a development accelerator such as a quaternary salt or amine, and the like.
• a pH buffer such as a sulfite, carbonate or borate of an alkali metal, a halogen salt or organic antifoggant, a water softener, a preservative, an organic solvent such as benzyl alcohol, ethylene glycol, etc.
• a development accelerator such as a quaternary salt or amine, and the like.
• the color developing process is usually followed by the bleach-fix process.
• the bleaching process may take place either simultaneously with or sparately from the fixing process.
• the bleaching agent to be used in the bleaching or bleach-fix process includes those compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), copper (II), etc,., and persulfates, and the like; for example, ferrocyanides, bichromates, organic complex salts of iron and cobalt, ethylenediaminetetraacetic acid, nitrilotriacetic acid, persulfates, permanganates, and the like, may be used.
• the processing method of this invention may apply to various types of commercially available light-sensitive materials to prevent them from producing a fog.
• the method may apply to those light-sensitive materials for general black-and-white use, for X-ray recording use, for graphic arts use, for low-speed positive use, for color positive use, for color negative use, for color paper use, for reversal color use, for direct positive use, for the diffusion transfer process, for the thermal development process, and the like.
• the method is particularly effectively applicable to the rapid development process that is to take place at a high temperature of not less than 30° C.
• any known antifoggants may be used in combination with the antifoggant of this invention.
• the usable antifoggants include those compounds wellknown to those skilled in the art, such as, e.g., 5-nitrobenzimidazole, 6-nitroindazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 2-mercaptobenzothiazole, and the like.
• a compound having the following Formula (II) (hereinafter called Compound II) is particularly desirable to be used in combination.
• Compound II a compound having the following Formula (II)
• Q is a group of atoms, including a carbon atom, a nitrogen atom, a sulfur atom or an oxygen atom, necessary to form a 5- or 6-member heterocyclic ring, and the ring formed by the Q is allowed to be condensed further with a hydrocarbon ring or another heterocyclic ring
• Z is an aromatic group or a heterocyclic group.
• the 5- or 6-member heterocyclic ring formed by the Q is a nitrogen-containing heterocyclic ring containing a carbon, nitrogen, sulfur or oxygen atom as the ring-consituting atom, and further the ring may be condensed with a hydrocarbon ring or with another heterocyclic ring;
• examples of the ring include imidazole, triazole, tetrazole, pyridine, pyrimidine, triazine, thiazole, oxazole, thiadiazole, oxadiazole, benzimidazole, benzothiazole, benzoxazole, purine, triazaindene, tetrazaindene, pentazaindene, and the like.
• heterocyclic rings each may have a substituent, such as, for example, a halogen atom, a hydroxyl, mercapto, amino, nitro, carboxyl, sulfo, alkyl, alkoxy, aryloxy, alkylthio, arylthio, carbamoyl, sulfamoyl, or the like group.
• a substituent such as, for example, a halogen atom, a hydroxyl, mercapto, amino, nitro, carboxyl, sulfo, alkyl, alkoxy, aryloxy, alkylthio, arylthio, carbamoyl, sulfamoyl, or the like group.
• the aromatic group represented by the Z is preferably a phenyl group or a naphthyl group. These phenyl and naphthyl groups each may also have a substituent, such as, for example, a halogen atom, a hydroxyl, mercapto, amino, nitro, alkyl, alkoxy, or the like group.
• the heterocyclic group represented by the Z may also be condensed, examples of which include imidazolyl, thiazolyl, pyridyl, pyrimidinyl, piperidinyl, benzothiazolyl, quinolyl, and the like groups. These heterocyclic groups each may also have a substituent, such as, e.g., a halogen atom, a hydroxyl, amino, nitro, alkyl, alkoxy, or the like group.
• the preferred ones among the compounds having Formula [II] are those of which the heterocyclic ring formed by the Q is imidazole, triazole, or tetrazole.
• the particularly preferred one is of tetrazole.
• the aromatic group represented by the Z is more preferably a phenyl, tolyl or m-nitrophenyl group, and the heterocyclic group is more preferably a 2-imidazolyl, 2-pyridyl or 2-benzothiazolyl group.
• the compounds having the foregoing Formula [I] are especially excellent in their fog restrainability in the light-sensitive material's long-period preservation under a high temperature-high humidity condition (about 50°-60° C./60-90% RH) rather than merely under a high temperature condition (about 50°-60° C.).
• the adding quantity of each of both compounds having Formula [I] and Formula [II], when added to a silver halide emulsion, is preferably in the range of from 10 -6 to 10 -1 mole per mole of the silver halide contained in the emulsion, and more preferably from 10 -5 to 10 -2 mole.
• the compounds having Formula [I] and Formula [II] each is in the quantity range of from 10 -5 mole to 1 mole in the coating liquid on a support per m 2 , and more preferably from 10 -4 to 10 -1 mole.
• Both compounds [I] and [II] may be used in a wide proportional range such as of from 1:0.01 to 1:100 by weight, but preferably from 1:0.1 to 1:50 by weight.
• the silver halide light-sensitive material to which this invention is applied may use any arbitrary silver halides for usual use in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, and the like.
• the silver halide grains usable in the silver halide emulsion may be ones obtained by any of the acid process, neutral process and ammoniacal process. These grains may be grown either at once or after the preparation of seed grains. The method of preparing seed grains and that of growing the grains may be either the same or different.
• the silver halide emulsion may be prepared either by mixing halide and silver ions simultaneously or by mixing either one into a liquid in which the other is present. Also, the halide ion and silver ion may be poured sequentially simultaneously, taking into account the critical growth rate of silver halide grains, into a mixing pot with the pH and/or pAg thereinside being controlled. By this method, silver halide grains in the regular crystal form with their grain size nearly uniform can be obtained. After the growth the halogen composition of the obtained grains may be changed by use of the conversion method.
• the silver halide emulsion may have the grain size, grain form, grain size distribution and grain growth rate thereof controlled, if necessary at the time of the manufacture thereof, by use of a silver halide solvent.
• the silver halide grain may contain metallic elements in the inside and/or on the surface thereof by adding thereto metallic ions, in the course of forming and/or growing the grain, by using at least one salt selected from the group consisting of cadmium salts, zinc salts, lead salts, thalium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts), and may be provided in the inside and/or on the surface thereof with a reduction sensitization nucleus by being place in an appropriate reductive atmosphere.
• the silver halide emulsion after completion of the growth of the silver halide grains therof, may have the useless water-soluble salt either removed therefrom or remain thereinside. If desired to remove the salt, the removal can be made in accordance with the method described in Research Disclosure (hereinafter abbreviated to RD) No. 17643 Item II.
• the silver halide grain although it may be one having a uniform silver halide composition distribution thereinside, but is particularly desirable to be a core/shell type grain whose inside and surface stratusm are different in the silver halide composition.
• the core/shell type silver halide emulsion is of a structure consisting of two or more strata different in the silver iodide content; the largest-amount silver iodide-containing stratum (called “core”) is other than the surface stratum (called “shell”).
• the core/shell type emulsion suitably usable for the light-sensitive material to be used in this invention is one in which the silver iodide content of the largest-amount silver iodide-containing inside stratuem (core) is from 6 to 40 mole %, more preferably from 8 to 30 mole %, and most preferably from 10 to 20 mole %.
• the silver iodide content of the surface stratum is preferably less than 6 mole %, and more preferably from zero to 4.0 mole %.
• the proportion of the shell portion to the core/shell type silver halide grain should account for preferably 10 to 80%, more preferably 15 to 70%, and most preferably 20 to 60%.
• the core portion should account for preferably 10 to 80% of the whole grain, and more preferably 20 to 50%.
• the difference in the silver iodide content between the large-amount silver iodide-containing core portion and the small-amount silver iodide-containing shell portion may either be sharply defined or not necessarily be clearly defined, continuously changing in the silver iodide content.
• one having a medium-amount silver iodide-containing intermediate stratum between the core and shell portions may also be suitably used.
• the preferred volume of the intermediate stratum accounts for 5 to 60% of the whole grain, and more preferably 20 to 55%.
• each of the differences in the silver iodide content between the shell and the intermediate stratum and between the intermediate stratum and the core is preferably not less than 3 mole %, and the difference in the silver iodide content between the shell and the core is preferably not less then 6 mole %.
• the core/shell type silver halide emulsion is of silver iodobromide whose silver iodide content is preferably from 4 to 20 mole %, and more preferably from 5 to 15 mole %.
• the emulsion may also contain silver chloride as long as it does not hurt the effect of this invention.
• the above-mentioned core/shell type emulsion may be prepared in accordance with those prior-art methods as disclosed in Japanese Patent O.P.I. Publication Nos. 177535/1984, 138538/1985, 52238/1984, 14331/1985, 35726/1985, 258536/1985, and the like.
• the grain can have in its center a silver halide composition region different from the core.
• the halide composition of the seed grain although it may be any arbitrary composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride or the like, should preferably be of silver iodobromide whose silver iodide content is not more than 10 mole % or silver bromide.
• the seed silver halide grains should account for preferably not more than 50% of the whole silver halide, and most preferably not more than 10%.
• the distribution condition of the silver iodide in the foregoing core/shell type silver halide grains can be detected in accordance with various measuring methods, and can be investigated by the luminescence measurement at a low temperature or the X-ray diffraction method as described in the substance book of the annual lecture meeting 1981 of the Society of Photographic Science and Technology of Japan.
• the core/shell type silver halide grain may be of either a regular crystal such as a cubic, tetradecahedral or octahedral crystal, or a twin. And the grain may also be a mixture of these crystals, but is desirable to be a regular crystal.
• the silver halide grain may be grown in the presence of a know silver halide solvent such as ammonia, thioether, thiourea, or the like.
• the silver halide grain, including the core/shell type grain, contained in the light-sensitive material to be used in the method of this invention may contain metallic elements in the inside and/or on the surface thereof by adding thereto, in the course of forming and/or growing the grain, metallic ions, using at least one salt selected from the group consisting of cadmium salts, zinc salts, lead salts, thalium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts), and also may be provided in the inside and/or on the surface thereof with a reduction sensitization nucleus.
• the silver halide emulsion after completion of the growth of the silver halide grains thereof may have the useless water-soluble salt either removed therefrom or remain thereinside.
• the removal may be made in accordance with the method described in RD 17643, Item II.
• the silver halide grain may be either one that a latent image is mainly formed on the surface thereof or one that a latent image is mainly formed thereinside.
• the usable silver halide grain size should be from 0.05 to 30 ⁇ , and preferably from 0.1 to 20 ⁇ .
• the silver halide emulsion used may be of any grain size distribution.
• a wide grain size distribution-having emulsion (called polydisperse emulsion) may be used, and differently narrower grain size distribution-having emulsions may also be used alone or in a mixture thereof.
• a polydisperse emulsion and a monodisperse emulsion may be used in a mixture thereof, but the emulsion used herein is desirable to be a monodisperse emulsion.
• the monodisperse emulsion is desirable to be one in which the weight of the silver halide thereof whose grain sizes are within the size range of the average grain size r ⁇ 20% accounts for not less than 60% of the weight of the whole silver halide, more preferably not less than 70%, and most preferably not less than 80%.
• the average grain size r is defined as the grain size ri when the ni ⁇ ri 3 , the product of the frequency ni of the grain having a grain diameter ri with ri 3 , becomes maxium. (Effective number of three figures, the minimum figure is rounded to the nearest whole number).
• the grain size herein in the case of a spherical silver halide grain, is defined as the diameter thereof and, where the grain is in the non-spherical form, is the diameter of a circular image into which is converted the projection image of the grain image of the same area.
• the grain diameter can be obtained, for example, in the manner that the grain's image is magnified by an electron microscope to a 10,000 to 50,000 times-enlarged photo and the diameter or the projected area of the grain's image of the obtained print is actually measured. (The number of the grains to be measured should be not less than 1000 taken at random.)
• the particularly preferred highly monodisperse emulsion in this invention when the width of the grain size distribution thereof is defined by ##EQU1## is one whose distribution width is not more than 20%, and more preferably not more than 15%, wherein the average grain size and the standard deviation are found from the ri as defined previously.
• the monodisperse emulsion can be obtained by adding an aqueous silver salt solution and an aqueous halide solution to a gelatin solution containing seed grains by the double-jet method under the control of pAg and pH.
• the silver halide emulsion may be used in a mixture of two or more separately formed silver halide emulsions.
• the siler halide emulsion may be chemically sensitized in usual manner; i.e., by using alone or in combination the sulfur sensitization method, selenium sensitization method, reduction sensitization method, noble-metal sensitization method which uses gold or other noble-metallic compounds, and the like.
• the silver halide emulsion may be optically sensitized to desired wavelength regions by using dyes known as sensitizing dyes to the photographic field. Those sensitizing dyes may be used either alone or in combination of two or more of them.
• a supersensitizer a dye which itself has no spectrally sensitizing function or a compound which does substantially not absorb visible rays but enhances the sensitization function of sensitizing dyes, may be incorporated along with such sensitizing dyes into the silver halide emulsion.
• cyanine dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
• the particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
• nuclei usually utilized as the basic heterocyclic nucleus in cyanine dyes the said nuclei including pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and nuclei formed by fusing alicyclic hydrocarbon rings to these nuclei, and nuclei formed by fusing aromatic hydrocarbon rings to these nuclei; i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus,
• a 5- or 6-member heterocyclic nucleus as one having a ketomethylene structure, such as pyrazoline-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, or the like.
• Useful sensitizing dyes for a blue-sensitive silver halide emulsion layer are those as described in, e.g., West German Patent No. 929,080, U.S. Pat. Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572, British Pat. No. 1,242,588, Japanese Patent Examined Publication No. 14030/1969 and 24844/1977, and the like.
• Useful sensitizing dyes for a green-sensitive silver halide emulsion are those typical cyanine dyes, merocyanine dyes or complex cyanine dyes as described in, e.g., U.S. Pat. Nos. 1,939,201, 2,072,908, 2,739,149, 2,945,763, and the like.
• useful sensitizing dyes for a red-sensitive silver halide emulsion are those typical cyanine dyes, merocyanine dyes or complex cyanine dyes as described in, e.g., U.S. Pat. Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,629, 2,776,280, and the like.
• those cyanine dyes, merocyanine dyes or complex cyanine dyes as described in U.S. Pat. Nos. 2,213,995, 2,493,748 and 2,519,001, and West German Pat. No. 929,080, and the like, may be advantageously used for a green-sensitive or red-sensitive silver halide emulsion.
• sensitizing dyes may be used either alone or in combination.
• the combination of these sensitizing dyes is often used particularly for the purpose of supersensitization. Examples representative of it are described in Japanese Patent Examined Publication Nos. 4932/1968, 4933/1968, 4936/1968, 32753/1969, 25831/1970, 26474/1970, 11627/1971, 18107/1971, 8741/1972, 11114/1972, 25379/1972, 37443/1972, 28293/1973, 38406/1973, 38407/1973, 38408/1973, 41203/1973, 41204/1973, 6207/1974, 40662/1975, 12375/1978, 34535/1979 and 1569/1980, Japanese Patent O.P.I.
• those dyes which in themselves have no spectral sensitization function or materials which do substantially not absorb visible rays but show supersensitization effects and which are usable along with the above sensitizing dyes are, for example, those aromatic organic acid-formaldehyde condensates (as described in, e.g., U.S. Pat. No. 3,473,510), those cadmium salts, azaindene compounds, nitrogen-containing heterocyclic group-substituted aminostilbene compounds (as described in, e.g., U.S. Pat. Nos. 2,933,390 and 3,635,721), and the like.
• the combined use described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly useful.
• any of those compounds known as antifoggants or stabilizers to those skilled in the art may be used along with the foregoing compound [I] or [II] during, upon completion of and/or after completion of the chemical ripening prior to the coating of the silver halide emulsion.
• Examples of the usable antifoggant or stabilizer include azoles such as benzothiazole, nitroindazole, benzotriazole, nitrobenzimidazole, etc., mercapto-substituted heterocyclic compounds such as mercaptobenzothiazole, mercaptobenzimidazole, mercaptobenzoxazole, mercaptooxadiazole, mercaptothiadiazole, mercaptotriazole, mercaptotriazine, mercaptotetrazoles (such as 1-phenyl-5-mercaptotetrazole), those wherein sulfonic acid group or carboxy group is introduced to the above mercaptoheterocyclic compouns, and further azaindenes such as 4-hydroxy-1,3,3a,7-tetrazaindene; those thiazolium salts as described in U.S.
• azoles such as benzothiazole, nitroindazole
• Gelatin is advantageously usable as the binder (or protective colloid) for the silver halide emulsion, and gelatin derivatives, graft polymers of gelatin with other high-molecular materials, other proteins, sugar derivatives, cellulose derivatives, hydrophilic colloid materials such as synthetic hydrophilic high-molecular homo- or co-polymer materials may also be used.
• Photographic emulsion layers and other hydrophilic colloid layers of the light-sensitive material of this invention may be hardened by using alone or in combination hardening agents that cross-link the binder (or protective colloid) molecular to enhance the strength thereof.
• the hardening agent may be added in a quantity so enough to harden the light-sensitive material that the hardening agent need not be added to the processing solution, but the hardening agent is also allowed to be added to the processing solution.
• plasticizer for the purpose of increasing the elasticity.
• the preferred plasticizers are those compounds described in RD 17643 XII A.
• Into photographic emulsion layers and other hydrophilic colloid layers of the light-sensitive material may be incorporated water-insoluble or less-soluble synthetic polymer-dispersed product (latex) for the purpose of improving the dimensional stabilization thereof.
• latex water-insoluble or less-soluble synthetic polymer-dispersed product
• the emulsion layer of the light-sensitive material may contain a dye-forming coupler which, in the color developing process, forms a dye by the coupling reaction thereof with the oxidized product of an aromatic primary amine developing agent (such as a p-phenylenediamine drivative, aminophenol derivative, etc.).
• the dye-forming coupler is usually selected so as to form a dye to absorb an appropriate spectral light which each individual emulsion is sensitive to; an yellow dye-forming coupler is used for the blue-sensitive emulsion layer, a magenta dye-forming coupler is used for the green-sensitive emulsion layer, and a cyan dye-forming coupler is used for the red-sensitive emulsion layer.
• a silver halide color photographic light-sensitive material is allowed to be prepared otherwise, using a different combination than the above according to purposes.
• These dye-forming couplers are desirable to have in the molecule thereof a group called ⁇ ballasting group ⁇ having not less than 8 carbon atoms to make them nondiffusible.
• These dye-forming couplers each may be either of the four-equivalent type, which requires 4 molecules of silver ions to be reduced for the formation of one molecule of the dye, or of the two-equivalent type, which requires only two molecules of silver ions to be reduced.
• dye-forming couplers include those compounds which, as a result of coupling with the oxidized product of a developing agent, release photographically useful fragments such as development inhibitors, development accelerators, bleaching accelerators, developing agents, silver halide solvents, color control agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizing agents.
• DIR coupler the coupler which, in the development process, releases a development accelerator to improve the sharpness and graininess of images.
• a DIR compound may be used which effects a coupling reaction with the oxidized product of a developing agent to produce a colorless compound and at the same time releases a development inhibitor.
• DIR couplers and DIR compounds to be used include those with which an inhibitor is directly combined in the coupling position thereof and those with which an inhibitor is combined through a divalent group in the coupling position thereof, the said inhibitor being combined so as to be released as a result of the intramolecular nucleophilic reaction or intramolecular electron-transfer reaction inside the molecule that has been split off by the coupling reaction (these are called “timing DIR couplers” and “timing DIR compounds”).
• Such inhibitors include those well-diffusible after the split-off and those relatively less-diffusible, which may be used alone or in combination.
• acylacetanilide-type couplers may be suitably used as the yellow dye-forming couplers.
• couplers benzoylacetanilide-type and pivaloylactanilide-type compounds are advantageous.
• Phenol or naphthol-type couplers are generally used as the cyan dye-forming coupler.
• magenta coupler examples include 5-pyrazone-type couplers, pyrazolobenzimidazole-type couplers, open-chain acylacetanilide-type couplers, indazolone-type couplers, and the like, but the processing method of this invention is particularly effective when the light-sensitive material contains a pyrazoloazole-type magenta coupler having the following Formula [M-I].
• Pyrazoloazole-type couplers although excellent in the color reproducibility as compared to those conventional pyrazolone-type couplers, have been considered disadvantageous in respect of increasing fog due to its high color-forming efficiency. The application of this invention can remarkably improve this disadvantage.
• Z 1 is a group of nonmetallic atoms necessary to form a nitrogen-containing heterocyclic ring, the ring formed by the Z 1 being allowed to have a substituent
• X 1 is a hydrogen atom or a group splittable in the reaction with the oxidized product of a color developing agent
• R is a hydrogen atom or a substituent.
• Examples representative of the substituent represented by the R include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and the like groups, and in addition, halogen atoms, cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio groups, and spiro compound
• the preferred alkyl groups represented by the R are those having from 1 to 32 carbon atoms, which may be either straight-chain or branched-chain.
• the preferred aryl group represented by the R is a phenyl group.
• the acylamino groups represent by the R include alkyl carbonylamino groups, arylcarbonylamino groups, and the like.
• the sulfonamido groups represented by the R include alkylsulfonylamino groups, arylsulfonylamino groups, and the like.
• alkyl and aryl components in the alkylthio and arylthio groups represented by the R include those alkyl groups and aryl groups as mentioned above.
• the preferred alkenyl groups represented by the R are those having from 2 to 32 carbon atoms, and the cycloalkyl groups are those having from 3 to 12 carbon atoms, and preferably from 5 to 7 carbon atoms.
• the alkenyl groups may be either straight-chain or branched-chain.
• the preferred cycloalkenyl groups represented by the R are those having from 3 to 12 carbon atoms, and particularly preferably from 5 to 7 carbon atoms.
• the sulfonyl groups represented by the R include alkylsulfonyl groups and arylsulfonyl groups, and the like.
• the sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups and the like.
• the phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, arylphosphonyl groups, and the like.
• the acyl groups include alkylcarbonyl groups, arylcarbonyl groups, and the like.
• the carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, and the like.
• the sulfamoyl groups include alkylsulfamoyl groups, arylsulfamoyl groups, and the like.
• the acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, and the like.
• the carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, and the like.
• the ureido groups include alkylureido groups, arylureido groups, and the like.
• the sulfamoylamino groups include alkylsulfamoylamino groups, arylsulfamoylamino groups, and the like.
• the preferred heterocyclic groups are those 5 to 7-member groups, whch include, e.g., 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like.
• the preferred heterocyclic oxy groups are those having a 5 to 7-member heterocyclic ring, which include, e.g., 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyl-tetrazole-5-oxy group, and the like.
• the preferred heterocyclic thio groups are those 5 to 7-member heterocyclic thio groups, which include, e.g., 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, and the like.
• the siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, and the like.
• the imido groups include succinic acid imido group, 3-heptadecyl-succinic acid imido group, phthalimido group, glutarimido group, and the like.
• the spiro compound residues include spiro[3,3]heptane-1-yl, and the like.
• the cross-linked hydrocarbon compound residues include bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.1 37 ]decane-1-yl, 7,7-dimethyl-bicyclo[2.2.1]heptane-1-yl, and the like.
• Examples of the group represented by the X 1 that can be split off by the reaction with the oxidized product of a color developing agent include halogen atoms (such as chlorine atom, bromine atom, fluorine atom) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nitrogen-containing heterocyclic ring to be combined through a nitrogen atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and ##STR7## (wherein R 1 ' is as defined in the foregoing R; Z 1 ' is as defined in the foregoing Z; and R 2 ' and R 3 '
• the foregoing nitrogen-containing heterocyclic ring represented by the Z 1 or Z 1 ' is a pyrazole ring, imidazole ring, triazole ring or tetrazole ring, or the like, and the substituent which the above ring may have includes those as defined in the foregoing R.
• R 1 through R 8 and X 1 are as defined in the previously mentioned R and X, respectively.
• Couplers having Formula [M-I] are those represented by the following Formula [M-VIII]: ##STR9## wherein R 1 , X 1 and Z 2 are as defined in the R, X 1 and Z 1 of the foregoing Formula [M-I], respectively.
• magenta couplers having Formulas [M-II] through [M-VII] are those represented by the Formula [M-II].
• R 9 is as defined in the foregoing R.
• R 9 is a hydrogen atom or an alkyl group.
• the substituent which may be introduced to the ring formed by the Z of Formula [M-I] and to the ring formed by the Z 1 of Formula [M-VIII] and the R 2 through R 8 of Formulas [M-II] through [M-VI] are preferably those represented by the following Formula [M-X]:
• R 1 is an alkylene group
• R 2 is an alkyl, cycloalkyl or aryl group.
• the alkylene group represented by the R 1 is one whose straight-chain portion has preferably not less than 2 carbon atoms, and more preferably 3 to 6 carbon atoms, and which may be either straight-chain or branched-chain.
• the cycloalkyl group represented by the R 2 is preferably 5- to 6-member one.
• couplers may be synthesized by making reference to the Journal of the Chemical Society, Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, Japanese Patent O.P.I. Publication Nos. 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985, 190779/1985, and the like.
• any of the above couplers of Formula [M-I] may be used in the quantity range of from 1 ⁇ 10 -3 to 1 mole per mole of the silver halide which is present in the emulsion containing the coupler, and more preferably from 1 ⁇ 10 -2 to 8 ⁇ 10 -1 mole.
• couplers may be used along with other different magenta couplers.
• a compound which reacts with the oxidized product of a color developing agent but provides no image density i.e., DP' scavenger can be used.
• the compound are those hydroquinone derivatives (Formula (H)), pyrogallol derivatives, catechol derivatives and resorcinol derivatives (Formula (P)), sulfonylamino derivatives (Formula (S)), and coupling-type compounds (Formula (Cs)): ##STR11## wherein Rh 1 and Rp 1 each is a hydrogen atom, an aliphatic or acyl group, provided that the Rh 1 and Rp 1 may be either the same or different; m of Formula (P) is 2 or 3, provided, where m is equal to 2, one of the two ORp 1 is in the o-position and the other is in the m-position and, where m is 3, the three ORp 1 s are combined with the benzen ring in positions adjacent to
• the aliphatic group represented by the Rh 1 or Rp 1 includes those having a substituent, such as an alkyl group or alkenyl group, or the like.
• the acyl group represented by the Rh 1 or Rp 1 is, for example, an alkylcarbonyl group or arylcarbonyl group.
• the monovalent group is, for example, a halogen atom, an aliphatic group, cycloalkyl group, aromatic group, alkylthio group, carbamoyl group, cyano group, formyl group, aryloxy group, acyloxy group, carboxyl group or a salt thereof, sulfo group or a salt thereof, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, CORh 3 , CORp 3 , SO2Rh 4 , SO2Rp 4 , CONHRh 5 , CONHRp 5 , or NHCORh 6 , NHCORp 6 , wherein Rh 3 , Rp 3 , Rh 4 , Rp 4 , Rh 5 , Rp 5 , and Rh 6 , Rp 6 represent aliphatic
• the alkyl group represented by the Rs 1 or Rs 2 may be either straight-chain or branched-chain, and is preferably one having from 1 to 30 carbon atoms.
• the aryl group represented by the Rs 1 or Rs 2 is preferably one having from 6 to 30 carbon atoms.
• the heterocyclic group represented by the Rs 1 or Rs 2 is preferably one having at leas one of O and N as hetero atoms and having from 5 to 30 carbon atoms.
• the amino group represented by the Rs 1 or Rs 2 includes those substituted by an alkyl or aryl group.
• the hydrogen atom of the hydroxyl group is substituted by a blocking group that is to be removed when coming into contact with an alkali.
• a typical blocking group is a group removable by hydrolysis or by intramolecular nucleophilic reaction.
• Typical groups removable by hydrolysis are acyl groups such as, e.g., aliphatic and aromatic carbonyl and sulfonyl groups.
• Typical examples of the group removable by intramolecular nucleophilic reaction are described in U.S. Pat. No. 4,310,612.
• the group represented by the Rs 2 includes those having a substituent.
• the coupling-type DP' scavenger compounds represented by Formula (Cs) include those of the following types:
• Couplers wherein the dye formed by the coupling reaction with the oxidized product of a color developing agent is dissolved out into the processing solution.
• Couplers which effect the coupling reaction thereof with the oxidized product of a color developing agent but remain in the leuco form.
• Couplers wherein the dye formed by the coupling reaction with the oxidized product of a color developing agent shows no significant visible ray absorption and provides a substantially colorless product.
• COUP 1 is a coupler mother nucleus having a coupling position (marked with *);
• BALL is a group which is combined with the COUP 1 in the coupling position thereof and splittable from the COUP 1 by the reaction with the oxidized product of a color developing agent and which is also a stabilization group having such a magnitude and form as to make the compound of Formula (Cs-I) nondiffusible;
• SOL is a solubilization group which is combined with the COUP 1 in the coupling position thereof and which, during or after the color development, provides transferability to the coupling product produced by the coupling reaction with the oxidized product of a color developing agent so as to dissolve out of the light-sensitive material system.
• the coupler mother nucleus represented by the COUP 1 includes any of these coupler mother nuclei known to or used by those skilled in the art for use in the formation of colored or colorless reaction products by the coupling reaction with the oxidized product of a color developing agent.
• BALL is a stabilization group having such a magnitude and form as to make the compound having Formula (Cs-I) nondiffusible, and useful examples thereof, although not restricted as long as it provides nondiffusibility to the compound of Formula (Cs-I), include those alkyl, aryl and heterocyclic groups having from 8 to 32 carbon atoms.
• These groups include those having a substituent that increases the nondiffusibility of, changes the reactability of, or causes the coupling reaction of the compound of Formula (Cs-I), and, after splitting off, increases the diffusibility of the BALL. Further, as the BALL such one is also preferred that is combined through a linkage group with the COUP 1 in the coupling position thereof.
• the solubilization group represented by the SOL is a group that makes the coupling product produced by the coupling reaction with the oxidized product of a color developing agent so transferable as to dissolve out of the light-sensitive materials system, and examples of the group included ionizable hydroxyl, carboxyl, sulfo and aminosulfonyl groups and ionizable salts and esters and ethers thereof, and the like.
• Those compounds wherein one or two or more of these groups are combined with the COUP 1 in the noncoupling position thereof are also preferred, or wherein a solubilization group in which, for example, an alkyl group having from 1 to 10 carbon atoms or an aryl group having from 6 to 12 carbon atoms, having one or two or more of the above ionizable groups, is combined with the COUP 1 in the noncoupling position thereof may also be advantageously used.
• the particularly preferred solubilization groups include those alkyl groups having from 1 to 10 carbon atoms or aryl groups having from 6 to 12 carbon atoms containing a carboxyl, sulfo or ionizable salts thereof directly combined to the noncoupling position of COUP 1 or one or two or more carboxyl or sulfo groups or ionizable salts thereof combined directly or through an amino or carbonyl group to the noncoupling position of COUP 1 .
• suitably usable soluble yellow, magenta and cyan dye-formable DP' scavengers may be represented by the following Formulas (Cs-II) through (Cs-VII):
• Rc 1 is an aryl or alkyl group (particularly tertiary alkyl group);
• Rc 2 is the foregoing stabilization group (BALL);
• Rc 3 is the foregoing solubilization group (SOL);
• Rc 4 is a hydrogen atom or a halogen atom, an alkyl or alkoxy group; and
• n+m is equal to or less than 5 (provided that n ⁇ 0, m ⁇ 0, and, when n and m each is not less than 2, they may be either the same or different).
• Rc 2 is as defined in the Rc 2 of the foregoing Formula (Cs-II);
• Rc 5 is a solubilization group (SOL);
• Rc 6 is a hydrogen atom, a halogen atom, an alkyl, alkoxy or amino group;
• p is equal to or less than 5 (provided p ⁇ 0, and when p is not less than 2; the Rc 6 s may be either the same or different); either one of Rc 7 and Rc 8 is a solubilization group (SOL) and the other is a hydrogen atom, an alkyl, alkoxy, aryl or amino group; and
• Rc 9 and Rc 10 are as defined in the Rc 7 and Rc 8 , respectively, of Formula (Cs-IV).
• Rc 2 is as defined in the Rc 2 of Formula (Cs-II); at least one of Rc 11 and Rc 12 is the foregoing solubilization group (SOL) and the other is a hydrogen atom or a halogen atom, an alkyl, alkoxy or alkylamido group; q is equal to or less than 3 (provided q ⁇ 0); and Rc 13 is the foregoing solubilization group (SOL).
• alkyl, alkoxy and alkylamido groups each has from 1 to 8 carbon atoms
• aryl groups each has from 6 to 10 carbon atoms
• amino groups include primary, secondary and tertiary amino groups.
• substituents and stabilization groups include those further substituted by such a substituent as a halogen atom, a hydroxyl, carboxyl, amino, amido, carbamoyl, sulfamoyl, sulfonamido, alkyl, alkoxy or aryl group.
• Examples of the compound that belongs to the foregoing (2) include those having the following Formula (Cs-VIII): ##STR22## wherein COUP 2 is as defined in the COUP 1 of Formula (Cs-I); Rc 14 is a group that is combined with the COUP 2 in the coupling position thereof and is unable to split off by the reaction of the coupler of Formula (Cs-VIII) with the oxidized product of a color developing agent.
• the mother nucleus of the coupler represented by the COUP 2 includes those coupler mother nuclei mentioned in Formula (Cs-I).
• Examples of the group represented by the Rc 14 include alkyl, substitued alkyl, aryl, substitued aryl, alkenyl, cyano and the like groups.
• the preferred compounds having Formula (Cs-VIII) are those made nondiffusible by an alkyl, aryl or heterocyclic group having from 8 to 32 carbon atoms which is combined with the coupler mother nucleus represented by the COUP 2 in the noncoupling position thereof.
• Examples of the compound which belongs to the foregoing (3) include those having the following Formula (Cs-IX): ##STR23## wherein COUP 3 is a coupler mother nucleus which produces a substantially colorless product by the coupling reaction thereof with the oxidized product of a color developing agent; and Rc 15 is a group which is combined with the COUP 3 in the coupling position thereof and splittable from the COUP 3 as a result of the coupling reaction with the oxidized product of a color developing agent.
• Formula (Cs-IX) ##STR23## wherein COUP 3 is a coupler mother nucleus which produces a substantially colorless product by the coupling reaction thereof with the oxidized product of a color developing agent; and Rc 15 is a group which is combined with the COUP 3 in the coupling position thereof and splittable from the COUP 3 as a result of the coupling reaction with the oxidized product of a color developing agent.
• Rc 15 is as defined in the Rc 15 of Formula (Cs-IX);
• Rc 16 is a hydrogen atom, a halogen atom, an alkyl, aryl, alkoxy, acyloxy or heterocyclic group;
• X is a oxygen atom or ⁇ N--Rc 17 , wherein Rc 17 is an alkyl, aryl, hydroxyl, alkoxy or sulfonyl group;
• Z is a group of nonmetallic atoms necessary to form a 5- to 7-member carbocyclic ring (such as indanone, cyclopentanone, cyclohexanone, etc.) or a heterocyclic ring (such as piperidone, pyrrolidone, hydrocarbostyryl, etc.).
• Rc 15 , Rc 16 and X are as defined in the Rc 15 , Rc 16 and X, respectively, of Formula (Cs-X);
• Rc 18 is an alkyl, aryl, heterocyclic cyano, hydroxyl, alkoxy, aryloxy, heterocyclic oxy, alkylamino, dialkylamino or anilino group.
• Rc 15 is as defined in the Rc 15 of Formula (Cs-IX): and Rc 19 and Rc 20 are either the same or different, and each is an alkoxycarbonyl, carbamoyl, acyl, cyano, formyl, sulfonyl, sulfinyl, sulfamoyl or ammonium group or ##STR27## wherein A is a group of nonmetallic atoms necessary to form a 5- to 7-member heterocyclic ring (such as phthalimido, triazole, tetrazole, etc.
• Rc 15 is as defined in the Rc 15 of Formula (Cs-IX);
• Rc 21 is an alkyl, aryl, anilino, alkylamino or alkoxy group; and
• B is an oxygen atom, a sulfur atom or a imino group.
• Those compounds represented by Formulas (Cs-I) through (Cs-XIII) may be synthesized in accordance with those methods as described in Japanese Patent O.P.I. Publication Nos. 113440/1984, 171955/1984 and 82423/1977, British Pat. Nos. 914,145 and 1,284,649, U.S. Pat. Nos. 2,742,832, 3,227,550, 3,928,041, 3,958,993, 3,961,959, 4,046,574, 4,052,231, 4,149,886, and the like.
• the DP' scavenger may also be added to nonlight-sensitive layers such as intermediate layers, protective layer, yellow filter layer, antihalation layer, and the like.
• the adding amount of the DP' scavenger when added to a silver halide emulsion layer, is in the range of preferably from 1 ⁇ 10 -6 mole to 1 ⁇ 10 -1 mole per m 2 , and most preferably from 1 ⁇ 10 -5 mole to 2 ⁇ 10 -3 mole.
• the adding amount may be appropriately selected according to the type of the compound to be used.
• the adding amount range is preferably from 1 ⁇ 10 -6 to 1 ⁇ 10 -2 mole per m 2 , and more preferably from 1 ⁇ 10 -5 to 1 ⁇ 10 -3 mole.
• the incorporation of the DP' scavenger may be carried out in accordance with those known methods as described in, e.g., U.S. Pat. No. 2,322,027, and the like.
• those hydrophobic compounds may be dispersed by use of various methods such as the solid dispersion method, latex dispersion method, oil-in-water-type emulsification dispersion method, and the like. These methods may be appropriately selected to be used according to the chemical structure, and the like, of hydrophobic compounds such as couplers.
• those conventional methods of the prior art for use in dispersing hydrophobic additives such as couplers may be used, which are such that a hydrophobic compound is dissolved usually in a high-boiling solvent having a boiling point of not less that about 150° C., if necessary, in combination with a low-boiling solvent and/or water-soluble organic solvent, and then emulsifiedly dispersed into a hydrophilic binder such as an aqueous gelatin solution using a surfactant by a dispersing means such as a stirrer, homogenizer, colloid mill, flow-jet mixer, ultrasonic disperser, and the like, and after that, the dispersed product is added to an objective hydrophilic colloid. After or upon the dispersion, a process of removing the low-boiling solvent may be inserted.
• the high-boiling solvent those organic solvents having a boiling point of not less than 150° C. which do not react with the oxidized product of a developing agent, such as phenol derivatives, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, and the like, may be used.
• a developing agent such as phenol derivatives, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, and the like, may benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, and the like.
• a low-boiling or water-soluble organic solvent may be used in combination with or in place of the high-boiling solvent.
• the low-boiling and substantially water-insoluble organic solvent include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, and the like.
• water-soluble organic solvent examples include acetone, methyl-isobutyl ketone, ⁇ -ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, hexamethyl phosphoric triamide, diethylene glycol monophenylether, phenoxy ethanol, and the like.
• dye-forming couplers DIR couplers, DIR compounds, image stabilizers, anticolorstain agent, ultraviolet absorbing agents, brightening agents and the like have an acid group such as carboxylic acid, sulfonic acid, etc.
• they may be introduced in the aqueous alkaline solution form into a hydrophilic colloid.
• Those usable as the dispersion aid for use in dispersing into water a solution of a hydrophobic compound dissolved in a single low-boiling solvent or in a combined low-boiling and high-boiling solvent by mechanical or ultrasonic means include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
• an anticolorstain agent may be used.
• the anticolorstain agent may be either incorporated into the emulsion itself or into an intermediate layer provided between emulsion layers.
• the preferred as the anticolorstain agent include hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like.
• an image stabilizer may be used for preventing the produced dye image from being deteriorated.
• the preferred compounds as the image stabilizer include, e.g., hydroquinone derivatives, gallic acid derivatives, phenol derivatives and bis compounds thereof, hydroxychraman and spiro compounds thereof, hydroxychroman and spiro compounds thereof, piperidine derivatives, aromatic amine compounds, benzodioxane derivatives, benzodioxonol derivatives, silicon atom-containing compounds, thioether compounds, and the like.
• the light-sensitive material of this invention may contain in the hydrophilic colloid layers thereof such as the protective layer, intermediate layers and the like an ultraviolet absorbing agent for the purpose of preventing them from producing fog due to the charging by friction or preventing the resulting dye image from being deteriorated by UV rays.
• the light-sensitive material may use a formalin scavenger in order to prevent the deterioration of the magenta dye-forming coupler and the like due to formalin during the storage of the light-sensitive matrial.
• a dye or ultraviolet absorbing agent is incorporated into the hydrophilic colloid layers of the light-sensitive material, they may be mordanted by a mordant such as a cationic polymer.
• silver halide emulsion layers and other hydrophilic colloid layers of the light-sensitive material may be added compounds for altering the developability such as a development accelerator, development retarder, and the like, or a bleaching accelerator.
• the preferred compounds suitably usable as the development accelerator are those compounds as described in RD 17643, Item XXI B-D, and usable as the development retarder are those as described in RD 17643, Item XXI E.
• a black-and-white developing agent and/or the precursor thereof may also be used.
• the emulsion layers of the light-sensitive material may contain any of additives such as polyalkylene oxides or ethers or esters or derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives or the like.
• additives such as polyalkylene oxides or ethers or esters or derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives or the like.
• a brightening agent may be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and at the same time for making the stain in the white background inconspicuous.
• Those compounds suitably usable as the brightening agent are described in RD 17643, Item V.
• the light-sensitive material may be provided with auxiliary layers such as filter layers, an antihalation layer, and an antiirradiation layer. These layers and/or emulsion layers may contain a dye which is to be dissolved out or bleached in the course of the processing. Examples of such the dye include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.
• the silver halide emulsion layers and/or other hydrophilic colloid layers of the light-sensitive material may contain a matting agent for reducing the gloss of the light-sensitive material, improving the ease of retouching, preventing the stickiness of sheets of the light-sensitive material to each other, and the like.
• a lubricant may be added to the light-sensitive material for the purpose of reducing the sliding friction.
• an antistatic agent for the purpose of preventing static electricity.
• the antistatic agent may be used in the antistatic layer provided on the nonemulsion-layer side of the support of the light-sensitive material, and may also be used in the emulsion layer and/or in the nonemulsion protective colloid layer on the emulsion layer-coated side of the support.
• the suitably usable compounds as the antistatic agent are those as described in RD 17643, XIII.
• Various surface active agents may be used in the photographic emulsion layers and/or other hydrophilic colloid layers of the light-sensitive material for the purpose of improving the coatability, preventing static electricity, and improving the sliding friction, emulsification dispersion, photographic characteristics such as development acceleration, increasing contrast, sensitization, and the like.
• Materials usable as the support of the light-sensitive material of this invention include elastic reflective support materials such as paper laminated with or synthetic paper of ⁇ -olefin polymers such as polyethylene, polypropylene, ethylene/butene copolymer and the like; film made of semisynthetic or synthetic high-molecular materials such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamides, and the like; and those elastic support materials produced by providing a reflective layer on these films, glass plates, metallic or earthenware materials, and the like.
• elastic reflective support materials such as paper laminated with or synthetic paper of ⁇ -olefin polymers such as polyethylene, polypropylene, ethylene/butene copolymer and the like
• film made of semisynthetic or synthetic high-molecular materials such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, poly
• the hydrophilic colloid layer of the light-sensitive material after the support surface is at need subjected to a corona discharge, ultraviolet ray irradiation or frame treatment, may be coated directly on the support or coated on the support through one or more subbing layers for improving the surface adherence, property of preventing static electricity, dimensional stability, wear resistance, and/or other properties of the support.
• a viscosity-increasing agent may be used in the coating of the light-sensitive material for the purpose of improving the coatability.
• those additives which, if in advance added to the coating liquid, tend to cause gelling before coating because of being fast reactive, such as, for example, hardeners, are desirable to be mixed by means of a static mixer or the like into the coating liquid immediately before the coating.
• the extrusion coating method and curtain coating method which are capable of coating two or more layers simultaneously are particularly useful, and the packet coating method may also be used according to purposes.
• the coatin speed may be arbitrarily selected.
• the exposure of the light-sensitive material of this invention may be made by using electromagnetic waves in the spectral regions to which the emulsion layers constituting the light-sensitive material of this invention are sensitive.
• the light-sensitive material may be exposed to any known light sources including natural light (sunright), tungsten lamp light, fluorescent lamp light, mercury-vapor lamp light, xenon arc light, carbon arc light, xenon flash light, cathode-ray tube flying spot, various laser lights, light-emitting diode light, lights released from phosphors excited by electron beam, X rays, ⁇ rays, ⁇ rays, and the like.
• Exposure time may be in a very wide range of from much shorter exposure time than 1 microsecond such as from 100 nanosecond to 1 microsecond by use of, e.g., a cathode-ray tube or xenon flash light, not to speak of from 1 millisecond to 1 second usually used in ordinary cameras, to much longer exposure time than one second.
• the exposure is allowed to be made continuously or intermittently.
• a high-speed silver iodobromide emulsion for radiography use (containing 2.0 mole % silver iodide) was chemically ripened by the gold and sulfur sensitization method up to the time when the maximum sensitivity was obtained, and to this was added 1.0 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mole of silver halide, and then the ripening was stopped.
• the emulsion was divided into two equal parts. One part was reserved for comparative blank, and to the other were added compounds of this invention and comparative compounds, as shown in Table 1, to be adequately adsorbed thereinto, and appropriate amounts of saponin as a coating aid and of formalin as a hardening agent, whereby an emulsion was prepared.
• the obtained emulsion was coated uniformly on a subbed polyester base support so that the coating silver amount was 3 g/m 2 , and then dried, whereby samples (No. 1 through No. 14) were prepared.
• Processing Solution [A] for radiographic light-sensitive materials
• each fog value is a base density-deducted value
• each sensitivity value is a relative speed value to the speed of Comparative Blank Sample 1 regarded as 100, based on the sensitivity found in the position of fog+0.5
• each gamma value is the inclination of the straight line portion of a characteristic curve.
• a black colloidal silver-containing gelatin layer A black colloidal silver-containing gelatin layer.
• Coating amount of silver 1.0 g/m 2
• Coating amount of silver 0.5 g/m 2
• a gelatin layer containing polymethyl methacrylate particles (diameter 1.5 ⁇ m).
• the coupler in each layer was used in the emulsified form, which was prepared in the manner that the coupler was added to a solution of tricresyl phosphate and ethyl acetate, and to this was added sodium p-dodecylbenzenesulfonate as an emulsifier, and the mixture was heated to thereby dissolve the coupler, and mixed with a heated 10% gelatin solution and then emulsified by a colloid mill.
• Sensitizing Dye I Anhydro-5,5'-dichloro-3,3'-di( ⁇ -sulfopropyl)-9-ethyl-thiacarbocyanine-hydroxide pyridium salt.
• Sensitizing Dye II Anhydro-9-ethyl-3,3'-di( ⁇ -sulfopropyl)-4,5,4'5'-dibenzothiacarbocyanine-hydroxide triethylamine salt.
• Sensitizing Dye III Anhydro-9-ethyl-5,5'-dichloro-3,3-di-( ⁇ -sulfopropyl)oxacarbcyaninehydroxide sodium salt.
• Sensitizing Dye IV Anhydro-5,6,5'6'-tetrachloro-1,1'-diethyl-3,3'-di-( ⁇ -[ ⁇ -( ⁇ -sulfopropoxy)ethoxy]ethylimidazolocarbocyaninehydroxide sodium salt. ##STR32##
• the emulsion of each of the foregoing blank sample emulsion layers is one, to which, after the addition thereto of the foregoing sensitizing dye, was added a known ripening stop agent 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in a quantity of 1 g per mole of silver halide, and which was regarded as a blank emulsion.
• the invention's or comparative antifoggant was added to Layers 3, 4, 6, 7, 9 and 10 as shown in Table 2 and, after having the agent adequately adsorbed thereto, the coupler and tricresyl phosphate were added thereto as previously mentioned. After that, an appropriate amount of a hardener 2-hydroxy-4,6-dichlorotriazine sodium salt was added, whereby ten multicoated samples (No. 16 to No. 25) were prepared.
• each fog value is a base density-deducted value
• the sensitivity of each sample is a relative speed value to that of Comparative Sample No. 15 (which was left as it was at room temperature for two days) being regarded as 100.
• compositions of the processing solutions used in the processing steps are as follows:
• a high-speed silver iodobromide emulsion for radiography use similar to the one that was used in Example-1 was chemically ripened up to the time when the maximum sensitivity is obtained by the sulfur sensitization method, and after that to this was added 1.0 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mole of silver halide and an appropriate amount of saponin as a coating aid, thus preparing an objective emulsion.
• the obtained emulsion was coated uniformly on a subbed polyester base so that the coating amount of silver is 3 g/m 2 , whereby a film sample was obtained.
• a 7 mol% silver iodide-containing silver iodobromide emulsion whose mean silver halide grain size is 1.2 ⁇ was chemically ripened up to the time when the maximum sensitivity was obtained by using a gold and sulfur sensitizers.
• a coupler-dispersed liquid which was prepared in the manner that a solution obtained by mixing 80 g per mole of silver halide of a magenta coupler 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)benzamido]-5-pyrazolone and 2.5 g of a colored magenta coupler 1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone with 120 g of tricresyl phosphate and 240 ml of ethyl acetate and dissolved by heating was emulsifiedly dispersed into a solution of 5 g of sodium triisopropylnaphthalenesulfonate dissolved in 550
• the film sample after being exposed through an optical wedge in usual manner, was color-developed in accordance with the processing steps in Example-1, provided that to the color developer solution were added compounds of this invention and comparative compounds as shown in Table 4.
• a 2.0 mole% silver iodide-containing silver iodobromide emulsion was chemically ripened by the gold-sulfur sensitization method up to the time when the maximum sensitivity was obtained, whereby a high-speed silver iodobromide emulsion was obtained.
• the emulsion was divided into two equal parts, and to these parts of the emulsion were added compounds of this invention (by single use and combined use of those compounds of [I] or [II]) and comparative compounds and further appropriate amounts of formalin as a hardening agent and saponin as a coating aid.
• Example-1 Each sample was exposed through an ordinary sensitometric wedge, then developed and fixed in the same manner as in Example-1, washed and then dried, and subsequently measured with respect to the sensitivity and fog in the same manner as in Example-1.
• a high-speed silver iodobromide emulsion for negative use (containing 6.0 mole% silver iodide) having a mean grain size of 1.2 ⁇ was chemically ripened by the gold-sulfur sensitization method up to the time when the maximum sensitivity was obtained.
• the above-prepared emulsion was divided into 18 parts, and one part of them was taken as a blank. To the other parts were added the comparative compounds and compounds of this invention, respectively, as shown in Table 2, and, after they were sufficiently adsorbed, to each of these parts was added equaly an appropriate amount of a gelatin hardening agent sodium 2-hydroxy-4,6-dichlorotriazine, whereby silver halide emulsion samples were obtained.
• Example-5 The obtained film samples, after being subjected to the same forced deterioration tests as in Example-5, were each exposed through an optical wedge in usual manner, and then processed under the same conditions as in Example-1.
• each fog value is a base density-deducted value
• each speed value is a relative value to the speed regarded as 100 of the blank sample that was allowed to stand at room temperature for three days
• each gamma value represents the inclination of the straight-line portion of a characteristic curve.
• Multilayer color light-sensitive material samples (No. 71 to No. 87) were prepared by use of the same materials and the same method as in Example-2.
• Sample 71 is a comparative sample containing no antifoggant.
• Samples 72 through 87 are ones to which were added Compounds [I], [II] of this invention or comparative compounds as antifoggants as shown in Table 7. The addition of these antifoggants was made to Emulsion Layers 3, 4, 6, 7, 9 and 10 of each sample.
• Example-2 Each of the obtained multilayer color light-sensitive material samples, after being subjected to the same preservability test treatment as in Example-1, was exposed through an optical wedge in usual manner, and then color-processed in the same manner as in Example-2.
• each fog value is a base density-deducted value
• each speed value is a relative value to the speed regarded as 100 of the blank sample (No. 71) that was allowed to stand at room temperature for three days.
• HC-1 Antihalation layer
• a black-colloidal silver-containing gelatin layer A black-colloidal silver-containing gelatin layer
• Layer 3 Low-speed red-sensitive silver halide emulsion layer (RL-1):
• Sensitizind Dye II . . .
• Cyan Coupler (C-3) . . .
• Layer 4 High-speed red-sensitive silver halide emulsion layer (RH-1):
• Coating amount of silver 1.3 g/m 2
• Cyan Coupler (C-5) . . .
• a gelatin layer the same as Layer 2.
• Layer 6 Low-speed green-sensitive silver halide emulsion layer (GL-1):
• Emulsion-I . . . Coating amount of silver 1.5 g/m 2
• Magenta coupler (Exemplified Compound 4) . . .
• Layer 7 High-speed green-sensitive silver halide emulsion layer (GH-1):
• Emulsion-II . . . Coating amount of silver 1.4 g/m 2
• Magenta coupler (Exemplified Compound 4) . . .
• CM-2 Colored Magenta Coupler
• Layer 8 Yellow filter layer (YC-1):
• Layer 9 Low-speed blue-sensitive silver halide emulsion layer (BL-1):
• AgBrI monodisperse emulsion (Emulsion III), mean grain size 0.48 ⁇ m, containing 6 mole% AgI . . . .
• AgBrI monodisperse emulsion (Emulsion IV), mean grain size 0.8 ⁇ m, containing 7 mole% AgI . . . .
• Coating amount of silver 0.5 g/m 2
• Layer 11 First protective layer (Pro-1):
• Coating amount of silver 0.5 g/m 2 , and
• UV-1 and UV-2 Ultraviolet Absorbing Agents UV-1 and UV-2.
• Layer 12 Second protective layer (Pro-2):
• gelatin hardening agents (H-1) and (H-2) and a surface active agent were added to each of the above layers.
• Sensitizind Dye I the same as the Sensitizing Dye I used in Examle-2.
• Sensitizing Dye II the same as the Sensitizing Dye II used in Example-2.
• Sensitizing Dye V Anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide.
• Sensitizing Dye VI Anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5'6'-dibenzoxacarbocyanine hydroxide.
• Sensitizing Dye VII Anhydro-3,3'-di-(3-sulfopropyl)-4,5-benzo-5'-methoxycyanine hydroxide. ##STR38##
• Sample 91 was prepared in the above manner, and further Samples No. 92 through No. 104 were prepared in similar manner except that the coupler-dispersed product in the Layer 7 of Sample 91 was replaced as given in Table 8 or Compounds [I] were newly added for the fog-prevention purpose to Layers 6 to 8.
• the coupler-dispersed liquid was added in the same amount, and Compound [I] in an amount of 1 ⁇ 10 -4 mole/mole of AgX to Layer 7 and 4 ⁇ 10 -3 /mole AgX to Layers 6 to 8, and Compound [II] in an amount of 2 ⁇ 10 -3 mole/mole of AgX.
• the color image formed on each of the above-processed Samples No. 91 to No. 104 was measured by means of a densitometer to find the green fog value and green color sensitivity thereof.
• the sensitivity of each sample was found in terms of a relative speed to the speed of the non-treated Sample 91 regarded as 100, provided however that, in each 55° C./22%RH-treated sample, its fog value was expressed in terms of ⁇ fog value (55° C./22%RH-nontreatment) and the relative speed was expressed in variation percent, [(55° C./22%RH treatment/nontreatment)-1] ⁇ 100.
• compositions-having respective layers were formed on a triacetyl cellulose film support in order from the support side to prepare a Sample 105, and multilayer color light-sensitive material Samples No. 105 through No. 117 were prepared with the Sample 105 regarded as reference as in Example-8.
• a black colloidal silver-containing gelatin layer A black colloidal silver-containing gelatin layer
• Layer 3 Low-speed red-sensitive silver halide emulsion layer (RL-2):
• AgBrI monodisperse emulsion V mean grain size (r) 0.80 ⁇ m, containing 9 mole% AgI, and AgBrI monodisperse emulsion (Emulsion VI), mean grain size (r) 0.4 ⁇ m, containing 8 mole%
• AgI . . . Coating amount of silver 1.7 g/m 2 .
• Cyan Coupler (C-3) . . .
• Layer 5 Low-speed green-sensitive silver halide emulsion layer (GL-2): ##STR40## Sensitizing Dye III . . . 1.9 ⁇ 10 -4 mole per mole of silver
• Magenta coupler (Exemplified Compound 4) . . .
• CM-2 Colored Magenta Coupler
• Layer 7 Low-speed blue-sensitive silver halide emulsion layer (BL-2):
• a gelatin layer containing an emulsified product of D-5 A gelatin layer containing an emulsified product of D-5.
• Layer 9 High-speed red-sensitive silver halide emulsion layer (RH-2):
• Cyan Coupler (C-5) . . .
• Layer 11 High-speed green-sensitive silver halide emulsion layer (GH-2):
• Magenta coupler (Exemplified Compound 4) . . .
• CM-2 Colored Magenta Coupler
• Emulsion-IX and Emulsion-V and AgBrI monodisperse emulsion mean grain size 0.08 ⁇ m, containing 1.0 mole% AgI . . .
• Layer 15 Second protective layer (Pro-4):
• Sample No. 105 was thus prepared, and further Compounds [I] or [II] were newly combinedly added to Layers 5, 11 and 12 of the Sample No. 105 for the fog prevention purpose, whereby Samples No. 106 through No. 117 were prepared.
• these antifoggants were added in an amount of 1 ⁇ 10 -3 mole/mole of AgX to Layers 5 and 11, and of 4 ⁇ 10 -4 mole/mole of AgX to Layer 12.
• the adding amount thereof is 2 ⁇ 10 -3 mole/mole of AgX, and 7 ⁇ 10 -4 mole/m 2 to Layer 12.
• the adding amount of the above antifoggant used in the comparative sample was 20 mg/mole of AgX.
• the color image formed on each of the processed Samples No. 105 to No. 117 was measured by use of a densitometer to thereby find the green fog value and green sensitivity thereof, provided however that, in the 55° C./22%RH-treated sample, the fog value was expressed in terms of ⁇ fog value (55° C./22%RH treatment-nontreatment) and the relative speed was expressed in terms of variation percent. [(55° C./22%RH treatment/nontreatment)-1] ⁇ 100.
• the Samples No. 106 to No. 117 of this invention are highly sensitive and excellent in restraining the possible increase in fog and deterioration of the sensitivity by heat during the storage thereof.
• the Samples 91, 92, 96 and 99 that were used in Example-8 were each cut into 35 mm wide ⁇ 120 cm long-size pieces and loaded into several film cartridges at the same time in the dark.
• the respective samples measured using a red light to find their fog values and the respective fog values' variation widths, i.e., the values obtained by deducting the fog value of the sample that was left for seven days at 5° C. from the values of the samples that were left for seven days at 60° C., are shown in Table 10.
• the Sample 121 was prepared in the same manner as that of Sample 91 in Example-8 except that the Layer 2 and Layer 8 contain no emulsified dispersion product of 2,5-dioctyl-hydroquinone.
• the color image formed on each of the processed Samples No. 121 to No. 141 was measured by a densitometer using a red light to find the fog value and sensitivity to red thereof.
• the sensitivity is a value of the reciprocal of the exposure that provides the minimum density+0.1 and is expressed in a relative value to the value of Sample 121 regarded as 100.
• the dye image of each sample having a density of Dmin+0.6 obtained by measuring using a red light was scanned by the 250 ⁇ m 2 -area circular head of a microdensitometer, and the 1000-fold value of the standard deviation of the variation of the desity values obtained by the microdensitometer scanning is shown in terms of a relative value of each sample to the value of Sample 121 as regarded as 100.
• the results are shown in Table 11.
• Sample 142 was used as the reference sample, the following compositions-having layers were formed on a triacetyl cellulose film support in order from the support side, whereby multilayer color light-sensitive material samples were prepared.
• Sample 142 (reference)
• a black colloidal silver-containing gelatin layer A black colloidal silver-containing gelatin layer
• Layer 3 Low-speed red-sensitive silver halide emulsion layer (RL-2):
• AgBrI monodisperse emulsion V mean grain size (r) 0.80 ⁇ m, containing 9 mole% AgI and AgBrI monodisperse emulsion (Emulsion VI), mean grain size (r) 0.4 ⁇ m, containing 8 mole%
• Cyan Coupler (C-3) . . .
• Layer 5 Low-speed green-sensitive silver halide emulsion layer (GL-2): ##STR44## Sensitizing Dye III . . . 1.9 ⁇ 10 -4 mole per mole of silver
• CM-2 Colored Magenta Coupler
• Layer 7 Low-speed blue-sensitive silver halide emulsion layer (BL-2):
• Layer 9 High-speed red-sensitive silver halide emulsion layer (RH-2):
• Cyan Coupler (C-3) . . .
• Layer 11 High-speed green-sensitive silver halide emulsion layer (GH-2):
• AgBrI monodisperse emulsion (Emulsion IX), means grain size (r) 1.6 ⁇ m, containing 9.0 mole% AgI . . . .
• CM-2 Colored Magenta Coupler
• Emulsion-IX and Emulsion-V and AgBrI monodisperse emulsion means grain size 0.08 ⁇ m
• Layer 14 First protective layer (Pro-3):
• UV-1 and UV-2 Ultraviolet Absorbing Agents UV-1 and UV-2.
• Layer 15 Second protective layer (Pro-4):
• the Samples No. 129, 130, 138 and 140 which were used in Example-11 were each cut into several 3.5 cm wide ⁇ 120 cm long size pieces, and these pieces were loaded into film cartridges at the same time in the dark.
• A-1 Two different twin-crystal emulsions, as shown in Table 16, having a uniform silver iodide composition (called A-1, 2) were prepared in the following manner:
• seed crystal grains having a silver iodide content of 2.0 mole% and grain sizes of 0.10 ⁇ and 0.30 ⁇ were prepared by the acid method.
• the seed emulsion was used to prepare, making reference to Japanese Patent O.P.I. Publication Nos. 48521/1979 and 49938/1983, core and shell by the double-jet method with the pAg and pH being controlled in the presence of ammonia.
• the grain size was adjusted by the selection of seed grains and the adding amount of silver, and the compositions of the core, intermediate stratum, and shell were adjusted by changing the composition of the halide solution to be added.
• B-6 and B-8 the growth of the grains thereof was made in the presence of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in a quantity of 0.15 g per mole of silver halide for the purpose of raising the monodispersibility.
• two other different monodisperse core/shell-type emulsions (called B-9 and 10) were prepared in the following manner: To an aqueous solution containing gelain and potassium bromide, with stirring at 40° C., was added a silver nitrate solution to thereby prepare a nucleus emulsion comprised of multitwin crystal grains, and then the emulsion was physically ripened in the presence of ammonia and potassium bromide, whereby a monodisperse spherical-type seed grain emulsion was obtained.
• This seed emulsion was used to prepare a core/shell emulsion with the pAg and pH controlled in the presence of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene by the double-jet method.
• the compositions of the core and shell were adjusted by changing the composition of the halide solution to be added. (Table 19)
• emulsions each was chemically ripened in a manner of the prior art, and also optically sensitized by using a sensitizing dye anhydro-3,3'-di-(3-sulfobutyl)-4,5-benzo-5-methoxythiocyanine, and then each emulsion was divided into several parts, and to these parts were added compounds of this invention, whereby high-speed blue-sensitive emulsions were prepare.
• Emulsions B-11 and B-12 shown in Table 20 were prepared in similar manner to the above described method
• HC-1 Antihalation layer
• a black colloidal silver-containing layer is provided.
• Layer 3 Low-speed red-sensitive silver halide emulsion layer (RL-1):
• Cyan Coupler (C-3) . . .
• Cyan Coupler (C-3) . . .
• a gelatin layer the same as Layer 2.
• Layer 6 Low-speed green-sensitive silver halide emulsion layer (GL-1):
• CM-2 Colored Magenta Coupler
• Layer 7 High-speed green-sensitive silver halide emulsion layer (GH-1):
• CM-2 Colored Magenta Coupler
• Layer 8 Yellow filter layer (YC-2)
• Layer 9 Low-speed blue-sensitive silver halide emulsion layer (BL-1):
• Emulsion An emulsion containing the emulsion shown in Table 20 and compounds of this invention . . . .
• Layer 11 First protective layer (Pro-1):
• a gelatin layer containing silver iodobromide (containing 1 mole% AgI; mean grain size 0.07 ⁇ m)
• Layer 12 Second protective layer (Pro-2):
• gelatin hardening agents (H-1) and (H-2) and a surface active agent in addition to the above compositions.
• Samples 161 to 187 each was exposed through an optical wedge to a white light, and then processed in the same manner as in Example-2. And those subjected to incubation treatment under the condition of 55° C./20%RH for 5 days were also processed in like manner. ##STR46##
• each relative speed is a value relative to the speed of Sample 161 regarded as 100. Also, as for the variation of the fog of each sample obtained after one part of the sample was treated for five days under the condition of 55° C./20%RH and exposed and the processed, the width of the variation of the fog of each sample is given in Table 21.
• the core/shell-type emulsion of this invention although its fog is slightly high, has a high sensitivity as compared to the comparative emulsion. However, the variation width of the fog after the incubation treatment is large.
• Example 22 The compounds of this invention shown in Table 22 were added to the respective layers of a multilayer color photographic element prepared in similar manner to that of Example-14, whereby Samples 188 through 195 were prepared, provided that the emulsion of Layer 10 is Emulsion-II of Example-14.
• Example 14 Each of the obtained samples, after being exposed through a wedge, was processed in the same manner as in Example-1. Those incubation-treated under the condition of 55° C./20%RH also were each processed in like manner. The processed samples were evaluated, and the results thereof are as given in Table 22. In Table 22, the relative speed, as defined in Example-14, is the relative value of each sample to that of Sample 188 regarded as 100.
• Emulsions B-13 and B-14 shown in Table 23 were prepared in the same manner as in Example-1.
• Sample 196 (Comparative):
• a black colloidal silver-containing gelatin layer A black colloidal silver-containing gelatin layer
• Layer 3 Low-speed red-sensitive silver halide emulsion layer (RL-2):
• Emulsion B-13 . . . .
• Cyan Coupler (C-3) . . .
• Layer 5 Low-speed green-sensitive silver halide emulsion layer (GL-2):
• Emulsion B-13 . . . .
• CM-2 Colored Magenta Coupler
• Layer 7 Low-speed blue-sensitive silver halide emulsion layer (BL-2):
• Emulsion B-13 . . . .
• Layer 9 High-speed red-sensitive silver halide emulsion layer (RH-2):
• Cyan Coupler (C-3) . . .
• Layer 11 High-speed green-sensitive silver halide emulsion layer (GH-2):
• CM-2 Colored Magenta Coupler
• Layer 12 Gelatin layer containing an emulsified product of 2,4-di-t-octylhydroquinone
• Layer 13 High-speed blue-sensitive silver halide emulsion layer (BH-2) :
• AgBrI monodisperse emulsion (Emulsion B-15), mean grain size 0.27 ⁇ m, containing 2 mole%
• Layer 14 First protective layer (Pro-3):
• UV-1 and UV-2 Ultraviolet Absorbing Agents UV-1 and UV-2.
• Layer 15 Second protective layer (Pro-4):
• gelatin hardening agents (H-1) and (H-2) and a surface active agent in addition to the above compositions.

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